Compositions, synthesis, and uses of hydrolyzable silane modified cashew nut shell liquid derivatives

ABSTRACT

The present disclosure provides cashew nut shell liquid derivatives based organosilicon products and methods and uses of preparing the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119 to U.S.Provisional Application No. 62/557,333, filed Sep. 12, 2017, which ishereby incorporated by reference in its entirety.

FIELD

The present embodiments relate to, in some embodiments, to the synthesisof novel cardanol-based derivatives through the introduction of silanefunctional groups. In some embodiments, the derivatives are used in 1Kand 2K formulations for coatings, adhesives, sealants and elastomersapplications.

BACKGROUND

Cashew nut shell liquid (CNSL) is one of the most widely used bio-basedresource to provide useful chemicals for coatings, adhesives, sealantsand elastomers (collectively “CASE”) applications. Cardanol is achemical derived by decarboxylation of anacardic acid which is theprimary component of CNSL. Cardanol is a meta substituted phenol ringwith mono-, di-, tri-unsaturated and saturated long 15 carbon chains, asshown, for example:

where R:

This illustrates the general structure of cardanol containing side chainwith varying number of unsaturation sites

The structure of cardanol is unique as it has an aromatic ring at oneend, which provides excellent rigidity, and the long chain at the metaposition, which provides a good moisture barrier. Cardanol has beenexplored extensively by derivatizing through the phenolic ring: A)reactive modification through phenolic OH, for e.g., epoxies etc., B)ortho and para substitution on the ring to provide different type ofreactive functionalities like amines, epoxies, polyols, amides etc.,(Lubi, M. C.; Thachil, E. T., Designed Monomers and Polymers (2000), 3,2, 123-153; Voirin, C.; Caillol, S.; Sadavarte, N. V.; Tawade, B. V.;Boutevin, B.; Wadgaonkar, P. P. Polym. Chem. (2014), 5, 3142-3162; A.Parambath, Cashew Nut Shell Liquid: a goldfield for functionalmaterials, Springer, 2017), each of which is incorporated by referencein its entirety.

The unsaturation sites present on the cardanol side chain have only alimited numbers of examples in the literature and mainly focus on theintroduction of hydroxyl and epoxy functionalities, acrylic, carboxylicor phosphorous containing groups or double bonds hydrogenation (Chen,Z.; Liu, R. US0345383; Ittara, S. K.; Sarangapani, K. WO2006003668;Prasad, V. S. N.; Pillai, C. K. S. WO2007077567; Madhusudhan, V.;Murthy, B. G. K. Prog. Org. Coatings, 20 (1992), 63-71; Perdriau, S.;Harder, S.; Heeres, H. J.; de Vries, J. G. ChemSusChem, 5 (2012),2427-2434), each of which is incorporated by reference in its entirety.

Accordingly, there is still a need to provide increased functionality tocardanol derivatives. The present disclosure provides for novelcompounds and methods of making the same that can be used in CASEapplications and other applications. The present application fulfillsthese needs as well as others.

SUMMARY

In some embodiments, a compound of Formula I is provided:

wherein:

A₁ is methylene; linear, branched and/or substituted alkyl (e.g. C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl); linear, branched and/or substituted aryl; linear, branchedand/or substituted phenyl; linear, branched and/or substituted alkenyl(e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄,C₂-C₄, or C₁-C₃ alkenyl); —CH₂—(NH-alkyl-NH₂), where alkyl (C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl) can be linear, branched and/or substituted;—CH₂—(NH-aryl-NH₂), where aryl can be linear, branched and/orsubstituted; —CH₂—(NH-phenyl-NH₂), where phenyl can be linear, branchedand/or substituted; —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H, where R₅can be H or CH₃; halogen; amino; azido; or nitro;

R is

R₁ is hydrogen, an epoxy, an alkyl, an ether or an ester group;

n is 1-20;

m is independently 0-20;

X₁ is independently a hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like;

X₂ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like; and

X₃ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like.

In some embodiments, a compound of Formula II is provided:

wherein:

A₁ is methylene; linear, branched and/or substituted alkyl (e.g. C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl); linear, branched and/or substituted aryl; linear, branchedand/or substituted phenyl; linear, branched and/or substituted alkenyl(e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄,C₂-C₄, or C₁-C₃ alkenyl); —CH₂—(NH-alkyl-NH₂), where alkyl (C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl) can be linear, branched and/or substituted;—CH₂—(NH-aryl-NH₂), where aryl can be linear, branched and/orsubstituted; —CH₂—(NH-phenyl-NH₂), where phenyl can be linear, branchedand/or substituted; —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H, where R₅can be H or CH₃; halogen; amino; azido; or nitro;

R is

wherein:

n is 1-20;

m is independently 0-20;

X₁ is independently a hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like;

X₂ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like; and

X₃ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like.

In some embodiments, a compound comprising one or more units of FormulaIII is provided:

wherein:

A₁ is methylene; linear, branched and/or substituted alkyl (e.g. C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl); linear, branched and/or substituted aryl; linear, branchedand/or substituted phenyl; linear, branched and/or substituted alkenyl(e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄,C₂-C₄, or C₁-C₃ alkenyl); —CH₂—(NH-alkyl-NH₂), where alkyl (C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl) can be linear, branched and/or substituted;—CH₂—(NH-aryl-NH₂), where aryl can be linear, branched and/orsubstituted; —CH₂—(NH-phenyl-NH₂), where phenyl can be linear, branchedand/or substituted; —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H, where R₅can be H or CH₃; halogen; amino; azido; or nitro;

-   -   R₁ is

-   -   R₂ is 3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane; and n is 1-20.

In some embodiments, a compound comprising one or more units of FormulaIV is provided:

wherein

-   -   R₂ is independently selected from the group of        3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane;        3-(N-phenylamino)-propyl-trimethoxysilane

In some embodiments, a compound of Formula V is provided:

wherein

-   -   R₃ is H; —CH₂CH(OH)-[3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane]    -   R₄ is

-   -   wherein Y is OH; 3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane; and    -   Z is OH; 3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane.

In some embodiments, methods of producing a compound or compositiondescribed herein is provided. In some embodiments, the method comprisesreacting a cardanol or a cardanol derivative with a hydrolyzable silaneunder suitable conditions to produce the compound. In some embodiments,the methods comprise reacting a cardanol substrate with an unsaturatedhydrolyzable silane in the presence of the free radical initiator at atemperature ranging from about 100° C. to about 350° C. under an inertatmosphere that is substantially free from water.

In some embodiments, a composition comprising any compound describedherein is provided. In some embodiments, the composition is an adhesionpromoter in an epoxy and polyurethane formulations, a fiber sizingagent, a rubber, a thermoplastic material, a self-curable polymer forhydrophobic coatings, or any combination thereof.

DETAILED DESCRIPTION

As used herein, the terms “a” or “an” means that “at least one” or “oneor more” unless the context clearly indicates otherwise.

As used herein, the term “alkyl” means a saturated hydrocarbon groupwhich is straight-chained or branched. An alkyl group can contain from 1to 20, from 2 to 20, from 1 to 10, from 2 to 10, from 1 to 8, from 2 to8, from 1 to 6, from 2 to 6, from 1 to 4, from 2 to 4, from 1 to 3, or 2or 3 carbon atoms. These can also be referred to the abbreviations ofC₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄,C₂-C₄, C₁-C₃, and the like. Examples of alkyl groups include, but arenot limited to, methyl (Me), ethyl (Et), propyl (e.g., n-propyl andisopropyl), butyl (e.g., n-butyl, t-butyl, isobutyl), pentyl (e.g.,n-pentyl, isopentyl, neopentyl), hexyl, isohexyl, heptyl,4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl,dodecyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl,3-methyl-1-butyl, 2-methyl-3-butyl, 2-methyl-1-pentyl,2,2-dimethyl-1-propyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl,2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl,2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, and thelike. These can also be referred to the abbreviations of C₁-C₂₀, C₂-C₂₀,C₁-C₆, and the like.

As used herein, the term “about” means that the numerical value isapproximate and small variations would not significantly affect thepractice of the disclosed embodiments. Where a numerical limitation isused, unless indicated otherwise by the context, “about” means thenumerical value can vary by ±10% and remain within the scope of thedisclosed embodiments. Additionally, in phrase “about X to Y,” is thesame as “about X to about Y,” that is the term “about” modifies both “X”and “Y.”

As used herein, the term, “compound” means all stereoisomers, tautomers,and isotopes of the compounds described herein.

As used herein, the terms “comprising” (and any form of comprising, suchas “comprise”, “comprises”, and “comprised”), “having” (and any form ofhaving, such as “have” and “has”), “including” (and any form ofincluding, such as “includes” and “include”), or “containing” (and anyform of containing, such as “contains” and “contain”), are inclusive oropen-ended and do not exclude additional, unrecited elements or methodsteps.

The term “halo” or “halogen” refers to fluoro, chloro, bromo, or iodo.In some embodiments, the halo groups are fluoro, chloro, and bromo. Insome embodiments, the halo groups are fluoro and chloro.

Substituted alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, or alkylthio,means an alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, or alkythio group,respectively, substituted one or more times independently with asubstituent selected from the group consisting of halo, hydroxy, andC₁-C₃ alkoxy or as provided for herein. By way of illustration, butwithout limitation, examples include trifluoromethyl, pentafluoroethyl,5-fluoro-2-bromopentyl, 3-hydroxypropyloxy, 4-hydroxycyclohexyloxy,2-bromoethylthio, 3-ethoxypropyloxy, 3-ethoxy-4-chlorocyclohexyl, andthe like. In some embodiments, substitutions include substitution 1-5times with halo, each independently selected, or substituted 1-3 timeswith halo and 1-2 times independently with a group selected from hydroxyand C₁-C₃ alkoxy, or substituted 1-3 times independently with a groupselected from hydroxy and C₁-C₃ alkoxy, provided that no more than onehydroxy and/or alkoxy substituent may be attached through the samecarbon.

As the term “aryl” is provided for herein it can be either a monocyclicaromatic group or a bicyclic aromatic group, which may containheteroatoms in the aromatic group (e.g. heteroaryl). The followingstructures are some non-limiting examples of representative aryl groups,but the aryl groups are not limited to those examples:

In some embodiments, the aryl group is not a heteroaryl group. In someembodiments, the aryl group is heteroaryl.

The terms “substituted phenyl”, “substituted aryl” and “substitutedheterocycle” are taken to mean that the cyclic moiety in either case issubstituted. They can be substituted independently with one or moresubstituents. They can be substituted independently with 1, 2, 3, 4, 5,1-3, 1-4, or 1-5 substituents or as provided for herein. Thesubstitution can be, independently, halo, alkyl, such as, but notlimited to, C₁-C₄ alkyl, alkoxy, such as but not limited to, C₁-C₄alkoxy, and alklylthio, such as but not limited to, C₁-C₄ alkylthio,wherein each alkyl, alkoxy and alkylthio substituent can be furthersubstituted independently with C₁-C₂ alkoxy or with one to five halogroups; or substituted with one substituent selected from the groupconsisting of phenyloxy, benzyloxy, phenylthio, benzylthio, andpyrimidinyloxy, wherein the phenyloxy, benzyloxy, phenylthio,benzylthio, and pyrimidinyloxy moiety can be further substituted withone to two substituents selected from the group consisting of halo,C₁-C₂ alkyl, and C₁-C₂ alkoxy; or substituted with one substituentselected from the group consisting of C₁-C₄ acyl and C₁-C₄alkoxycarbonyl, and further substituted with zero to one substituentselected from the group consisting of halo, C₁-C₄ alkyl, C₁-C₄ alkoxy,and C₁-C₄ alkylthio. When a substituent is halo, in some embodiments,the halo groups are fluoro, chloro, and bromo. The halo can also beiodo.

In some embodiments, cashew nut shell liquid derivatives (“CNSL”) basedorganosilicon products are provided by reacting the CNSL, whichincludes, for example, cardanol, with silanes, such as, but not limitedto, vinylsilanes. In some embodiments, these silylated-cardanolderivatives can be further modified to form suitable raw materials forcoatings and adhesives compositions, providing better adhesionproperties and moisture resistance. Methods for preparing suchorganosilicon products based on cardanol and its derivatives areprovided herein. The presently described compounds and methods of makingthe same, such as, but not limited to, silylated mono- andmultifunctional cardanol derivatives overcome the limitations ofexisting silylated natural oils. The presently described compoundsdemonstrate higher hardness and hydrophobicity due to the presence ofthe aromatic ring as well as improved hydrolytic stability due to theabsence of hydrolyzable bonds like ester groups. Additionally, theintroduction of silane groups on different position of thecardanol-backbone can provide different mechanical, thermal and cureproperties to the final formulated systems where the new derivatives areused, spacing from epoxy to polyurethane matrices to fibers sizingagents.

Cardanol is a meta substituted phenol obtained by treating cashew nutshell liquid (CNSL). It contains 15 carbon unsaturated aliphatic sidechain at the meta position. This aliphatic side chain may have eitherone, two or three carbon-carbon double bonds. This unsaturation can beused to derivatize useful chemicals from cardanol which can used forcoatings, adhesives, sealants, rubbers, elastomers etc. applications.

In some embodiments, cardanol or other cardanol derivatives can bereacted with alkene-terminated silanes through the unsaturation presenton the aliphatic side chain of the cardanol compound to produceorganosilicon materials that provide the useful properties of silanes aswell as cardanol. These products can be used for numerous applications.

In some embodiments, silylation through ‘ene’ type mechanism is used tograft silanes on non-terminal double bonds. The production of silanemodified cardanol derivatives due to the presence of the aromatic ringat one end of the unsaturated chain provides better mechanical strengthto the final product and therefore, can be used effectively for varietyof applications, whereas previous silane modified oils could be used inthe same manner. In some embodiments, the hydroxyl group present on thephenol ring of cardanol can react with the alkoxy groups of silane, andprovide added functionality on the molecule.

In some embodiments, cardanol's silylation reaction proceeds via ‘ene’mechanism, as shown in the following non-limiting scheme:

In some embodiments, in the presence of peroxide catalyst, thevinylsilane grafts on the unsaturation present on the long chain withoutconsuming the unsaturation, but simply shifting it to the next carbon.This is shown as a non-limiting example the schemes provided herein.

In some embodiments, the peroxide catalyst is as free radical initiator.In some embodiments, the peroxide catalyst is selected in the groupconsisting of benzoyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxide) hexane, bis-(methylbenzoyl)peroxide,bis(dimethylbenzoyl)peroxide, dicumylperoxide, t-butyl3-isopropenylcumyl peroxide, butyl 4,4-bis(tert-butylperoxy)valerate,bis(trimethylbenzoyl)peroxide, and combinations thereof. The catalystcan be one or a combination of different peroxide catalysts.

In some embodiments, the peroxide catalyst level is from about 0.2% toabout 3%, about 0.5% to about 2%, about 0.5% to about 1.5%, about 0.75%to about 1.25%, about 1% to about 2%, or about 1% w/w with respect tothe substrate (e.g. cardanol).

The silane coupling agent can be any suitable unsaturated silanecoupling agent. In some embodiments, the silane coupling agents has aformula of

wherein,

m is independently 0-20;

X₁, is a hydrolyzable group selected from chloro, methoxy, propoxy,methylalkoxy, acetoxy, silazanes, oximes, and the like;

X₂ is a saturated or unsaturated hydrocarbon chain of 1-20 carbon atoms,or is hydrolyzable group selected from chloro, methoxy, propoxy,methylalkoxy, acetoxy, silazanes, oximes, and the like;

X₃ is a saturated or unsaturated hydrocarbon chain of 1-20 carbon atoms,or is hydrolyzable group selected from chloro, methoxy, propoxy,methylalkoxy, acetoxy, silazanes, oximes, and the like.

Cardanol derivative/silane coupling agent molar ratio can range fromabout 1 to about 0.5, about 1 to 1, or about 1:2, including all ratiosin between. However these are only exemplary ratios and are not intendedto be limiting. Other combinations can be used and can be adjusteddepending on the specific reagents used.

In some embodiments, the silane coupling reaction is performed in apressurized vessel under an inert (e.g. nitrogen) atmosphere to preventhydrolysis. In some embodiments, the reaction is heated, which withoutbeing bound by any theory, improves conversion rates and yields. In someembodiments, the pressure can be from about 5 to about 20 bars. In someembodiments, the temperature can be from about 140° C. to 350° C.

Without being bound to any particular theory, under the conditionsdescribed herein, the ‘ene’ reaction can proceed in an efficient mannerdue to the fact that unsaturated hydrolyzable silanes do not undergothermal polymerization like common vinyl monomers such as styrene,acrylates and similar vinyl monomers. Additionally, cardanol containsvery minimal amount of completely saturated long chain which cannotparticipate in the silylation reaction through unsaturation, but stillcan react via phenolic OH group.

In some embodiments, the starting material is a cardanol derivative,such as cardanol glycidyl ether and cardanol epoxy derivatives. Forcardanol glycidyl ether and cardanol epoxy derivatives the silylationoccurs, for example, through the unsaturation present on the unsaturatedside chain as shown in the non-limiting scheme as illustrated here:

This example illustrates that the silane molecule does not react withthe epoxies present on the aromatic ring as in the case of phenolic OHpresent on cardanol. The final silylated product provides dualfunctionality; epoxy and alkoxysilane.

In addition to cardanol, other cardanol-derivatives suitable to rununsaturated hydrolyzable silanes addition through “ene” reaction can bealkylated cardanol (e.g. butylated cardanol), alkoxylated cardanolgrades with a number of ethylene oxide or propylene oxide units rangingfrom 1 to 20, mono and multifunctional epoxy derivatives (e.g. CardoliteNC-513, UL-513, NC-547, NC-514, GX-2551), cardanol derived esters,including acrylates and methacrylates. These are only non-limitingexamples of cardanol derivatives that can be used in an “ene” reactionand other can be used.

The purity of the starting cardanol and cardanol derivatives can varyfrom about 80% to about 99.5%, or 90% to about 95%.

The extent of unsaturated hydrolysable silanes can be quantified usingstandard analytical techniques. For example, with thermogravimetricanalysis (TGA) the sample can be isothermally heated at 130° C. (abovethe boiling point of silanes) for several minutes, and the unreactedsilane is measured based on the weight loss variation. Table 1 indicatesexamples of the number of moles of silane grafted calculated for thesilylation reaction with different molar ratios of cardanol and cardanolglycidyl ether with silane.

TABLE 1 examples of conversion of cardanol or cardanol- substrates tothe corresponding silylated derivatives molar ratio Reaction number ofmoles Substrate [substrate:silane] Temperature [° C.] of silane graftedCardanol 1:0.5 225 0.37 1:0.5 250 0.42 1:2   225 0.67 Cardanol 1:0.5 2250.31 Glycidyl 1:0.5 250 0.34 Ether 1:2   225 0.61

The findings from thermogravimetric analysis can be confirmed by gelpermeation chromatography (GPC) and high-performance liquidchromatography (HPLC) results.

In some embodiments, to further improve the conversion rate of thesilane addition on cardanol and cardanol derivatives side chain, apreliminary side chain activation step can be performed, by conjugatingthe double bonds by isomerization. Isomerization can be performed underany suitable conditions, such as described in WO2008131918, which ishereby incorporated by reference in its entirety.

In some embodiments, epoxidized cardanol derivatives (with the epoxygroups on the phenoxy OH or on the side chain double bonds or on boththe positions) are used as substrates to be reacted withamino-functional hydrolyzable silanes, the reaction is run under milderconditions with respect to previous derivatives.

In some embodiments, a non-limiting example of synthesis of anamino-functional hydrolyzable silane obtained from a cardanol-basedglycidyl ether (e.g. Cardolite NC-513 or Cardolite UL-513) can beperformed according to the following scheme:

In some embodiments, a non-limiting example of synthesis of amulti-amino-functional hydrolyzable silane obtained from acardanol-based di-functional glycidyl ether epoxy resin (e.g. CardoliteNC-514 or Cardolite NC-514S) can be performed according to the followingscheme.

In some embodiments, a non-limiting example of synthesis of amulti-amino-functional hydrolyzable silane obtained from acardanol-based epoxy resin (e.g. Cardolite GX-2551) can be performedaccording to the following scheme.

For example, in some embodiments, according to the schemes provided forherein or others apparent to one of skill in the art cardanol-basedepoxy derivatives can be reacted under nitrogen atmosphere with suitableamino-functional hydrolyzable silanes (or their combinations) in atemperature range from about 0° C. to about 90° C. or about 20° C. toabout 40° C. The amount of the silane nucleophiles is determined on thebasis of each substrates epoxy equivalent weight and desired conversion.Other conditions are possible depending on raw materials selection.

The moisture activated cure of alkoxy terminated is well known in theliterature and it is based on hydrolyzable Si—O—C linkages. Upon contactwith moisture, the Si—O—C linkages in the silylated product arehydrolyzed to form Si—OH (silanols), which further react with anothersuch silanols to form a flexible and stable Si—O—Si linkages bycondensation. This moisture cure is thus a two-step mechanism asschematically shown the following scheme. The reaction can occur at roomtemperature and by, for example, action of atmospheric moisture. Thatis, in some embodiments, no exogenous water is added to the reaction tocure the compound.

This scheme is a non-limiting example of moisture activated cure ofsilylated cardanol. Other schemes can also be used.

Cardanol is one of the most promising bio-based material used in thecoatings industry, by derivatizing through the aromatic ring andphenolic OH. Phenalkamines and Phenalkamides derived from cardanolcaptured a huge market as epoxy curing agents in the coatings industry.Also, cardanol glycidyl ether with epoxy functionality on cardanol hasbeen a popular bio-based substitute in the coatings, adhesivesindustries. Silylation provides an excellent opportunity to add one morefunctionality to these molecules using ‘under-utilized’ side chainunsaturation. Although the cure mechanism for silanes is quite differentthan traditional epoxy curing mechanism, it doesn't require any moreadditives and simply occurs just by utilizing atmospheric moisture.Interestingly, it adds the flexible and stable Si—O—Si (siloxane)linkages that could aid the physical properties of the final curedstructure when necessary. Silanes are very popular for the ability asadhesion promotor and providing excellent moisture resistance. Themultifunctionality provided by silylation to cardanol and itsderivatives, can be very vital for improving existing applicationattributes and as well as developing new applications.

In some embodiments, a compound comprising one or more units of theformula

wherein

A₁ is methylene; linear, branched and/or substituted alkyl (e.g. C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl); linear, branched and/or substituted aryl; linear, branchedand/or substituted phenyl; linear, branched and/or substituted alkenyl(e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄,C₂-C₄, or C₁-C₃ alkenyl); —CH₂—(NH-alkyl-NH₂), where alkyl (C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl) can be linear, branched and/or substituted;—CH₂—(NH-aryl-NH₂), where aryl can be linear, branched and/orsubstituted; —CH₂—(NH-phenyl-NH₂), where phenyl can be linear, branchedand/or substituted; —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H, where R₅can be H or CH₃; halogen; amino; azido; or nitro;

R₁ is hydrogen, an epoxy, an alkyl, an ether or an ester group;

n is 1-20; and

R is

wherein

m is independently 0-20;

X₁ is independently a hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like;

X₂ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like; and

X₃ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like.

In some embodiments, Al is methylene; linear, branched and/orsubstituted alkyl (e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈,C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, or C₁-C₃ alkyl). In some embodiments, thealkyl is C₁-C₂₀ alkyl. In some embodiments, the alkyl is C₂-C₂₀ alkyl.In some embodiments, the alkyl is C₂-C₁₀ alkyl. In some embodiments, thealkyl is C₁-C₈ alkyl. In some embodiments, the alkyl is C₂-C₈ alkyl. Insome embodiments, the alkyl is C₁-C₆ alkyl. In some embodiments, thealkyl is C₂-C₆ alkyl. In some embodiments, the alkyl is C₁-C₄ alkyl. Insome embodiments, the alkyl is C₂-C₄ alkyl. In some embodiments, thealkyl is C₁-C₃ alkyl.

In some embodiments, Al is linear, branched and/or substituted aryl;linear, branched and/or substituted phenyl; linear, branched and/orsubstituted alkenyl (e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆,C₂-C₆, C₁-C₄, C₂-C₄, or C₁-C₃ alkenyl). In some embodiments, the alkenylis C₁-C₂₀ alkenyl. In some embodiments, the alkenyl is C₂-C₂₀ alkenyl.In some embodiments, the alkenyl is C₂-C₁₀ alkenyl. In some embodiments,the alkenyl is C₁-C₈ alkenyl. In some embodiments, the alkenyl is C₂-C₈alkenyl. In some embodiments, the alkenyl is C₁-C₆ alkenyl. In someembodiments, the alkenyl is C₂-C₆ alkenyl. In some embodiments, thealkenyl is C₁-C₄ alkenyl. In some embodiments, the alkenyl is C₂-C₄alkenyl. In some embodiments, the alkenyl is C₁-C₃ alkenyl.

In some embodiments, Al is —CH₂—(NH-alkyl-NH₂), where alkyl (e.g.C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl) can be linear, branched and/or substituted. In someembodiments, the alkyl is C₂-C₂₀ alkyl. In some embodiments, the alkylis C₂-C₁₀ alkyl. In some embodiments, the alkyl is C₁-C₈ alkyl. In someembodiments, the alkyl is C₂-C₈ alkyl. In some embodiments, the alkyl isC₁-C₆ alkyl. In some embodiments, the alkyl is C₂-C₆ alkyl. In someembodiments, the alkyl is C₁-C₄ alkyl. In some embodiments, the alkyl isC₂-C₄ alkyl. In some embodiments, the alkyl is C₁-C₃ alkyl.

In some embodiments, Al is —CH₂—(NH-aryl-NH₂), where aryl can be linear,branched and/or substituted.

In some embodiments, Al is —CH₂—(NH-phenyl-NH₂), where phenyl can belinear, branched and/or substituted;

In some embodiments, Al is —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H,where R₅ can be H or CH₃; halogen; amino; azido; or nitro.

In some embodiments, a compound comprising one or more units of theformula is provided:

wherein:

A₁ is methylene; linear, branched and/or substituted alkyl (e.g. C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₂-C₆, C₂-C₄, or C₁-C₃ alkyl);linear, branched and/or substituted aryl; linear, branched and/orsubstituted phenyl; linear, branched and/or substituted alkenyl (e.g.C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄,C₂-C₄, or C₁-C₃ alkenyl); —CH₂—(NH-alkyl-NH₂), where alkyl (C₁-C₂₀,C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₂-C₈, C₂-C₆, C₂-C₄, or C₁-C₃ alkyl) can belinear, branched and/or substituted; —CH₂—(NH-aryl-NH₂), where aryl canbe linear, branched and/or substituted; —CH₂—(NH-phenyl-NH₂), wherephenyl can be linear, branched and/or substituted;—CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H, where R₅ can be H or CH₃;halogen; amino; azido; or nitro;

R is

wherein

n is 1-20;

m is independently 0-20;

X₁ is independently a hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like;

X₂ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like; and

X₃ is independently a saturated or unsaturated hydrocarbon chain of 1-20carbon atoms, or is hydrolyzable group selected from chloro, methoxy,propoxy, methylalkoxy, acetoxy, silazanes, oximes, and the like.

In some embodiments, Al is methylene; linear, branched and/orsubstituted alkyl (e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈,C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, or C₁-C₃ alkyl). In some embodiments, thealkyl is C₁-C₂₀ alkyl. In some embodiments, the alkyl is C₂-C₂₀ alkyl.In some embodiments, the alkyl is C₂-C₁₀ alkyl. In some embodiments, thealkyl is C₁-C₈ alkyl. In some embodiments, the alkyl is C₂-C₈ alkyl. Insome embodiments, the alkyl is C₁-C₆ alkyl. In some embodiments, thealkyl is C₂-C₆ alkyl. In some embodiments, the alkyl is C₁-C₄ alkyl. Insome embodiments, the alkyl is C₂-C₄ alkyl. In some embodiments, thealkyl is C₁-C₃ alkyl.

In some embodiments, Al is linear, branched and/or substituted aryl;linear, branched and/or substituted phenyl; linear, branched and/orsubstituted alkenyl (e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₂-C₈, C₂-C₆,C₂-C₄, or C₁-C₃ alkenyl). In some embodiments, the alkenyl is C₁-C₂₀alkenyl. In some embodiments, the alkenyl is C₂-C₂₀ alkenyl. In someembodiments, the alkenyl is C₂-C₁₀ alkenyl. In some embodiments, thealkenyl is C₁-C₈ alkenyl. In some embodiments, the alkenyl is C₂-C₈alkenyl. In some embodiments, the alkenyl is C₁-C₆ alkenyl. In someembodiments, the alkenyl is C₂-C₆ alkenyl. In some embodiments, thealkenyl is C₁-C₄ alkenyl. In some embodiments, the alkenyl is C₂-C₄alkenyl. In some embodiments, the alkenyl is C₁-C₃ alkenyl.

In some embodiments, Al is —CH₂—(NH-alkyl-NH₂), where alkyl (e.g.C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₂-C₈, C₂-C₆, C₂-C₄, or C₁-C₃ alkyl) canbe linear, branched and/or substituted. In some embodiments, the alkylis C₂-C₂₀ alkyl. In some embodiments, the alkyl is C₂-C₁₀ alkyl. In someembodiments, the alkyl is C₁-C₈ alkyl. In some embodiments, the alkyl isC₂-C₈ alkyl. In some embodiments, the alkyl is C₁-C₆ alkyl. In someembodiments, the alkyl is C₂-C₆ alkyl. In some embodiments, the alkyl isC₁-C₄ alkyl. In some embodiments, the alkyl is C₂-C₄ alkyl. In someembodiments, the alkyl is C₁-C₃ alkyl.

In some embodiments, Al is —CH₂—(NH-aryl-NH₂), where aryl can be linear,branched and/or substituted.

In some embodiments, Al is —CH₂—(NH-phenyl-NH₂), where phenyl can belinear, branched and/or substituted;

In some embodiments, Al is —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H,where R₅ can be H or CH₃; halogen; amino; azido; or nitro.

In some embodiments, a compound comprising one or more units of theformula is provided:

wherein:

-   -   A₁ is methylene; linear, branched and/or substituted alkyl (e.g.        C₁-C₆ alkyl); linear, branched and/or substituted aryl; linear,        branched and/or substituted phenyl; linear, branched and/or        substituted alkenyl (e.g. C₁-C₆ alkenyl); —CH₂—(NH-alkyl-NH₂),        where alkyl (e.g. C₁-C₆ alkyl) can be linear, branched and/or        substituted; —CH₂—(NH-aryl-NH₂), where aryl can be linear,        branched and/or substituted; —CH₂—(NH-phenyl-NH₂), where phenyl        can be linear, branched and/or substituted;        —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H, where R₅ can be H or        CH₃; halogen; amino; azido; or nitro;    -   R₁ is

-   -   R₂ is 3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane; and n is 1-20.

In some embodiments, Al is methylene; linear, branched and/orsubstituted alkyl (e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₂-C₁₀, C₁-C₈, C₂-C₈,C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, or C₁-C₃ alkyl). In some embodiments, thealkyl is C₁-C₂₀ alkyl. In some embodiments, the alkyl is C₂-C₂₀ alkyl.In some embodiments, the alkyl is C₂-C₁₀ alkyl. In some embodiments, thealkyl is C₁-C₈ alkyl. In some embodiments, the alkyl is C₂-C₈ alkyl. Insome embodiments, the alkyl is C₁-C₆ alkyl. In some embodiments, thealkyl is C₂-C₆ alkyl. In some embodiments, the alkyl is C₁-C₄ alkyl. Insome embodiments, the alkyl is C₂-C₄ alkyl. In some embodiments, thealkyl is C₁-C₃ alkyl.

In some embodiments, Al is linear, branched and/or substituted aryl;linear, branched and/or substituted phenyl; linear, branched and/orsubstituted alkenyl (e.g. C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆,C₂-C₆, C₁-C₄, C₂-C₄, or C₁-C₃ alkenyl). In some embodiments, the alkenylis C₁-C₂₀ alkenyl. In some embodiments, the alkenyl is C₂-C₂₀ alkenyl.In some embodiments, the alkenyl is C₂-C₁₀ alkenyl. In some embodiments,the alkenyl is C₁-C₈ alkenyl. In some embodiments, the alkenyl is C₂-C₈alkenyl. In some embodiments, the alkenyl is C₁-C₆ alkenyl. In someembodiments, the alkenyl is C₂-C₆ alkenyl. In some embodiments, thealkenyl is C₁-C₄ alkenyl. In some embodiments, the alkenyl is C₂-C₄alkenyl. In some embodiments, the alkenyl is C₁-C₃ alkenyl.

In some embodiments, Al is —CH₂—(NH-alkyl-NH₂), where alkyl (e.g.C₁-C₂₀, C₂-C₂₀, C₂-C₁₀, C₁-C₈, C₂-C₈, C₁-C₆, C₂-C₆, C₁-C₄, C₂-C₄, orC₁-C₃ alkyl) can be linear, branched and/or substituted. In someembodiments, the alkyl is C₂-C₂₀ alkyl. In some embodiments, the alkylis C₂-C₁₀ alkyl. In some embodiments, the alkyl is C₁-C₈ alkyl. In someembodiments, the alkyl is C₂-C₈ alkyl. In some embodiments, the alkyl isC₁-C₆ alkyl. In some embodiments, the alkyl is C₂-C₆ alkyl. In someembodiments, the alkyl is C₁-C₄ alkyl. In some embodiments, the alkyl isC₂-C₄ alkyl. In some embodiments, the alkyl is C₁-C₃ alkyl.

In some embodiments, Al is —CH₂—(NH-aryl-NH₂), where aryl can be linear,branched and/or substituted.

In some embodiments, Al is —CH₂—(NH-phenyl-NH₂), where phenyl can belinear, branched and/or substituted;

In some embodiments, Al is —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H,where R₅ can be H or CH₃; halogen; amino; azido; or nitro.

In some embodiments, a compound of the formula is provided:

wherein

-   -   R₂ is independently selected from the group of        3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; and 3-(N-phenyl        amino)-propyl-trimethoxysilane.

In some embodiments a compound having the formula of is provided:

wherein

-   -   R₃ is H; —CH₂CH(OH)-[3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine;        3-aminopropylmethyl-diethoxysilane;        3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane]    -   R₄ is

-   -   wherein Y is OH; 3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine; 3-aminopropyl        methyl-diethoxysilane; 3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane; and    -   Z is OH; 3-aminopropyltriethoxysilane;        bis[(3-triethoxysilyl)propyl]amine;        3-aminopropyltrimethoxysilane;        bis[(3-trimethoxysilyl)propyl]amine; 3-aminopropyl        methyl-diethoxysilane; 3-aminopropylmethyl-dimethoxysilane;        aminoethylamino-propyl-trimethoxysilane;        N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;        amino-ethyl-aminopropyl-triethoxysilane;        amino-ethyl-aminopropyl-methyl-dimethoxysilane;        diethylene-triamino-propyl-trimethoxysilane;        diethylene-triamino-propyl-methyl-dimethoxysilane;        piperazinyl-propyl-methyldimethoxysilane;        (N-phenylamino)-methyl-triethoxysilane; or        3-(N-phenylamino)-propyl-trimethoxysilane.

The compounds can be produced according to any of the schemes providedfor herein or that would otherwise produce the compounds. In someembodiments, the methods comprise reacting a cardanol or a cardanolderivative with a hydrolyzable silane under suitable conditions toproduce the compound.

In some embodiments, the methods comprise reacting a cardanol or acardanol derivative with a hydrolyzable silane in the presence of a freeradical initiator at a temperature ranging from about 100° C. to 350°C., under an inert atmosphere and at a pressure from about 5 to 20 bars.

In some embodiments, the methods comprise reacting a cardanol or acardanol derivative with a hydrolyzable silane at a temperature fromabout 0° C. to about 100° C., under an inert atmosphere, at an ambientpressure and without the use of any catalyst.

In some embodiments, the cardanol or cardanol derivative is cardanol, ormono and multifunctional cardanol-derived substrates, such as, but notlimited to, those provided for herein.

In some embodiments, the cardanol or cardanol derivative has a purityfrom about 80% to about 99%. In some embodiments, the purity is about90-99%, about 95- to about 99%, about 95, 96, 97, 98, or 99% pure. Insome embodiments, the purity is about 100%.

In some embodiments, the monomeric cardanol-derived starting material isa cardanol epoxy, an alkylated cardanol, an alkoxylated cardanol, acardanol allyl ether, an acrylated and methacrylated cardanol, anisomerized cardanol, or a cardanol based benzoxazines. In someembodiments, the cardanol derivative is a polymeric cardanol.

In some embodiments, the polymeric cardanol is a cardanol novolac, acardanol resole, or a cardanol-epoxy novolac. In some embodiments, thecardanol derivative is an epoxidized phenolated cardanol derivative. Insome embodiments, the cardanol is epoxy functionalized on the phenoxyOH, on the alkyl side chain, or on both positions.

In some embodiments, methods of producing a compound are provided, themethod comprising reacting a cardanol substrate with an unsaturatedhydrolyzable silane in the presence of the free radical initiator at atemperature ranging from about 100° C. to about 350° C. under an inertatmosphere that is substantially free from water. In some embodiments,the unsaturated silane isvinyltrimethoxysilane, vinyltriethoxysilane,vinyltriacetoxysilane, allyl(methoxy)dimethylsilane,allyltriisopropoxysilane, allylphenyldiphenoxysilane, and anycombinations thereof.

In some embodiments, the free radical initiator is a peroxide catalystin the group of benzoyl peroxide, di-t-butylperoxide,2,5-dimethyl-2,5-di (t-butylperoxide) hexane,bis-(methylbenzoyl)peroxide, bis(dimethylbenzoyl) peroxide,dicumylperoxide, t-butyl 3-isopropenylcumyl peroxide, butyl4,4-bis(tert-butylperoxy)valerate, bis(trimethylbenzoyl)peroxide, andany combinations thereof. These are non-limiting examples and other freeradical initiator can be used.

In some embodiments, the silane is an amino-functional silane. In someembodiments, the amino-functional silanes is selected from the groupconsisting of 3-aminopropyltriethoxysilane;bis[(3-triethoxysilyl)propyl]amine; 3-aminopropyltrimethoxysilane;bis[(3-trimethoxysilyl)propyl]amine; 3-aminopropylmethyl-diethoxysilane;3-aminopropylmethyl-dimethoxysilane;aminoethylamino-propyl-trimethoxysilane;N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;amino-ethyl-aminopropyl-triethoxysilane;amino-ethyl-aminopropyl-methyl-dimethoxysilane;diethylene-triamino-propyl-trimethoxysilane;diethylene-triamino-propyl-methyl-dimethoxysilane;piperazinyl-propyl-methyldimethoxysilane;(N-phenylamino)-methyl-triethoxysilane; and3-(N-phenylamino)-propyl-trimethoxysilane.

In some embodiments, the silane comprise a hydrolyzable group selectedfrom the group consisting of chloro, methoxy, propoxy, methylalkoxy,acetoxy, silazane, and oxime.

Embodiments provided herein also provide compositions comprising acompound as provided herein or a compound produced according toembodiments provided herein. In some embodiments, the composition is anadhesion promoter in an epoxy and polyurethane formulations, a fibersizing agent, a rubbers, a thermoplastic material, a self-curablepolymer for hydrophobic coatings, or any combination thereof.

The compounds and methods of making the same provided for in the presentapplication can be used in many methods/applications. Examples include,but not limited to, the use as a coupling agents for polymerapplications like thermosets, urethanes, epoxies, phenolics,thermoplastics, polyolefin, where the modification with silanes providesimproved adhesion and also more sites for reactivity. Additionalapplication opportunities include construction and packaging ofelectronic boards, paper packaging, food packaging where the moistureresistance ability of siloxane cured network will be applicable. Furtheropportunities include the use for surface modifications to provide morewettability to the surface and on the other end to provide superhydrophobic surfaces, self-cleaning surfaces with proper selection ofsilanes. In some embodiments, a composition comprising any compounddescribed herein is provided. In some embodiments, the composition is anadhesion promoter in an epoxy and polyurethane formulations, a fibersizing agent, a rubber, a thermoplastic material, a self-curable polymerfor hydrophobic coatings, or any combination thereof.

Other aspects and advantages of these silylated cardanol-derivedproducts will be apparent to those skilled in the art. Experimentaldetails are provided in the following examples, which are provided byway of illustration only and should not be construed to limit thedisclosure or the appended claims.

EXAMPLES Example 1: Silylation of Cardanol

420 gms. of cardanol (1.4 moles) was mixed with 207 gms. ofvinyltrimethoxysilane (1.4 moles) together in a high-pressurestainless-steel PARR reactor (PARR Instrument Company, IL, USA).Luperox-101 (6 gms., 1% w/w), used as a catalyst for this reaction, wasthen added to the reaction mixture. The reaction mixture was then purgedwith nitrogen for several minutes, to create inert environment. Thereactor was heated to 250° C. and kept it isothermally at thistemperature for 5 hours. The reactor was cooled down at the end of 5hours. The final weight of the product was measured, where a total yieldof 98.5% was calculated. The product was secured in an air-tight andmoisture-free container.

Example 2: Silylation of Cardanol Based Glycidyl Ether

The high-pressure reactor vessel (1 L) was charged with 427 gms. ofcardanol glycidyl ether (1.2 moles) and 178 gms. ofvinyltrimethoxysilane (1.2 moles), mixed together with Luperox-101 (6gms., 1% w/w) used as a catalyst. The reactor was purged with nitrogenfor several minutes. The silylation reaction was carried out at 250° C.for 5 hours. The reactor was cooled down at the end of 5 hours. At theend of the reaction, the product was secured in an air-tight, moisturefree container. The yield was found to be around 96.3%.

Example 3: Adduct of Silylated Cardanol Based Glycidyl Ether and Amine

51.5 gms (0.5 moles) of diethylenetriamine was added to a round bottomflask. It was kept under constant stirring with a nitrogen blanket overit for about 15 minutes. Then, 562 gms. (2 epoxy equivalent, EEW=562g/mol.) of cardanol based glycidyl ether was added to the flask and themixture was kept under constant stirring for 6 hours at 60° C. and witha nitrogen blanket above it. At the end of 6 hours, the reaction mixturewas cooled to 35° C.-40° C. and was secured in an air-tight and moisturefree container.

Various references and patents are disclosed herein, each of which arehereby incorporated by reference for the purpose that they are cited.

From the foregoing, it will be appreciated that various embodiments ofthe present disclosure have been described herein for purposes ofillustration, and that various modifications can be made withoutdeparting from the scope and spirit of the present disclosure.Accordingly, the various embodiments disclosed herein are not intendedto be limiting.

1. A compound comprising one or more units of the formula

wherein A₁ is methylene; linear, branched and/or substituted alkyl;linear, branched and/or substituted aryl; linear, branched and/orsubstituted phenyl; linear, branched and/or substituted alkenyl;CH₂—(NH-alkyl-NH₂), where alkyl can be linear, branched and/orsubstituted; —CH₂—(NH-aryl-NH₂), where aryl can be linear, branchedand/or substituted; —CH₂—(NH-phenyl-NH₂), where phenyl can be linear,branched and/or substituted; —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀ H,where R₅ can be H or CH₃; halogen; amino; azido; or nitro; R₁ ishydrogen, an epoxy, an alkyl, an ether or an ester group; n is 1-20; andR is

wherein m is independently 0-20; wherein: X₁ is independently ahydrolyzable group selected from chloro, methoxy, propoxy, methylalkoxy,acetoxy, silazanes, oximes, and the like; X₂ is independently asaturated or unsaturated hydrocarbon chain of 1-20 carbon atoms, or ishydrolyzable group selected from chloro, methoxy, propoxy, methylalkoxy,acetoxy, silazanes, oximes, and the like; and X₃ is independently asaturated or unsaturated hydrocarbon chain of 1-20 carbon atoms, or ishydrolyzable group selected from chloro, methoxy, propoxy, methylalkoxy,acetoxy, silazanes, oximes, and the like.
 2. A compound comprising oneor more units of the formula

wherein: A₁ is methylene; linear, branched and/or substituted alkyl;linear, branched and/or substituted aryl; linear, branched and/orsubstituted phenyl; linear, branched and/or substituted alkenyl;CH₂—(NH-alkyl-NH₂), where alkyl can be linear, branched and/orsubstituted; —CH₂—(NH-aryl-NH₂), where aryl can be linear, branchedand/or substituted; —CH₂—(NH-phenyl-NH₂), where phenyl can be linear,branched and/or substituted; —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H,where R₅ can be H or CH₃; halogen; amino; azido; or nitro; n is 1-20;and R is

wherein m is independently 0-20; X₁ is independently a hydrolyzablegroup selected from chloro, methoxy, propoxy, methylalkoxy, acetoxy,silazanes, oximes, and the like; X₂ is independently a saturated orunsaturated hydrocarbon chain of 1-20 carbon atoms, or is hydrolyzablegroup selected from chloro, methoxy, propoxy, methylalkoxy, acetoxy,silazanes, oximes, and the like; and X₃ is independently a saturated orunsaturated hydrocarbon chain of 1-20 carbon atoms, or is hydrolyzablegroup selected from chloro, methoxy, propoxy, methylalkoxy, acetoxy,silazanes, oximes, and the like.
 3. A compound comprising one or moreunits of the formula

wherein: A₁ is methylene; linear, branched and/or substituted alkyl(e.g. C₁-C₆ alkyl); linear, branched and/or substituted aryl; linear,branched and/or substituted phenyl; linear, branched and/or substitutedalkenyl (e.g. C₁-C₆ alkenyl); —CH₂—(NH-alkyl-NH₂), where alkyl (e.g.C₁-C₆ alkyl) can be linear, branched and/or substituted;—CH₂—(NH-aryl-NH₂), where aryl can be linear, branched and/orsubstituted; —CH₂—(NH-phenyl-NH₂), where phenyl can be linear, branchedand/or substituted; —CH₂—N—(CH₂CH—R₅—O)₂—(CH₂CH—R₅—O)₀₋₁₀—H, where R₅can be H or CH₃; halogen; amino; azido; or nitro; R₁ is

R₂ is 3-aminopropyltriethoxysilane; bis[(3-triethoxysilyl)propyl]amine;3-aminopropyltrimethoxysilane; bis[(3-trimethoxysilyl)propyl]amine;3-aminopropylmethyl-diethoxysilane; 3-aminopropylmethyl-dimethoxysilane;aminoethylamino-propyl-trimethoxysilane;N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;amino-ethyl-aminopropyl-triethoxysilane;amino-ethyl-aminopropyl-methyl-dimethoxysilane;diethylene-triamino-propyl-trimethoxysilane;diethylene-triamino-propyl-methyl-dimethoxysilane;piperazinyl-propyl-methyldimethoxysilane;(N-phenylamino)-methyl-triethoxysilane; or3-(N-phenylamino)-propyl-trimethoxysilane; and n is 1-20; or a compoundof the formula:

wherein R₂ is independently selected from the group of3-aminopropyltriethoxysilane; bis[(3-triethoxysilyl)propyl]amine;3-aminopropyltrimethoxysilane; bis[(3-trimethoxysilyl)propyl]amine;3-aminopropylmethyl-diethoxysilane; 3-aminopropylmethyl-dimethoxysilane;aminoethylamino-propyl-trimethoxysilane;N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;amino-ethyl-aminopropyl-triethoxysilane;amino-ethyl-aminopropyl-methyl-dimethoxysilane;diethylene-triamino-propyl-trimethoxysilane;diethylene-triamino-propyl-methyl-dimethoxysilane;piperazinyl-propyl-methyldimethoxysilane;(N-phenylamino)-methyl-triethoxysilane;3-(N-phenylamino)-propyl-trimethoxysilane; or. a compound having theformula of:

wherein: R₃ is H; —CH₂CH(OH)-[3-aminopropyltriethoxysilane;bis[(3-triethoxysilyl)propyl]amine; 3-aminopropyltrimethoxysilane;bis[(3-trimethoxysilyl)propyl]amine; 3-aminopropylmethyl-diethoxysilane;3-aminopropylmethyl-dimethoxysilane;aminoethylamino-propyl-trimethoxysilane;N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;amino-ethyl-aminopropyl-triethoxysilane;amino-ethyl-aminopropyl-methyl-dimethoxysilane;diethylene-triamino-propyl-trimethoxysilane;diethylene-triamino-propyl-methyl-dimethoxysilane;piperazinyl-propyl-methyldimethoxysilane;(N-phenylamino)-methyl-triethoxysilane; or3-(N-phenylamino)-propyl-trimethoxysilane. R₄ is

wherein Y is OH; 3-aminopropyltriethoxysilane;bis[(3-triethoxysilyl)propyl]amine; 3-aminopropyltrimethoxysilane;bis[(3-trimethoxysilyl)propyl]amine; 3-aminopropylmethyl-diethoxysilane;3-aminopropylmethyl-dimethoxysilane;aminoethylamino-propyl-trimethoxysilane;N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;amino-ethyl-aminopropyl-triethoxysilane;amino-ethyl-aminopropyl-methyl-dimethoxysilane;diethylene-triamino-propyl-trimethoxysilane;diethylene-triamino-propyl-methyl-dimethoxysilane;piperazinyl-propyl-methyl dimethoxysilane(N-phenylamino)-methyl-triethoxysilane; or3-(N-phenylamino)-propyl-trimethoxysilane; and Z is OH;3-aminopropyltriethoxysilane; bis[(3-triethoxysilyl)propyl]amine;3-aminopropyltrimethoxysilane; bis[(3-trimethoxysilyl)propyl]amine;3-aminopropylmethyl-diethoxysilane; 3-aminopropylmethyl-dimethoxysilane;aminoethylamino-propyl-trimethoxysilane;N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;amino-ethyl-aminopropyl-triethoxysilane;amino-ethyl-aminopropyl-methyl-dimethoxysilane;diethylene-triamino-propyl-trimethoxysilane;diethylene-triamino-propyl-methyl-dimethoxysilane;piperazinyl-propyl-methyl dimethoxysilane(N-phenylamino)-methyl-triethoxysilane; or3-(N-phenylamino)-propyl-trimethoxysilane. 4-5. (canceled)
 6. A methodproducing a compound according to claim 1, comprising reacting acardanol or a cardanol derivative with a hydrolyzable silane undersuitable conditions to produce the compound.
 7. A method of producing acompound according to claim 1, comprising reacting a cardanol or acardanol derivative with a hydrolyzable silane in the presence of a freeradical initiator at a temperature ranging from about 100° C. to 350°C., under an inert atmosphere and at a pressure from about 5 to 20 bars.8. A method of producing a compound according to claim 1 comprising, themethod comprising reacting a cardanol or a cardanol derivative with ahydrolyzable silane at a temperature from about 0° C. to about 100° C.,under an inert atmosphere, at an ambient pressure and without the use ofany catalyst.
 9. The method of claim 6, wherein the cardanol or cardanolderivative is cardanol, or mono or multifunctional cardanol-derivedsubstrates.
 10. The method of claim 6, wherein the number of repeatingunits in cardanol-derived substrate is 1 to about
 20. 11. The method ofclaim 6, wherein the cardanol has a purity from about 80% to about 99%.12. The method of claim 6, wherein the monomeric cardanol-derivedstarting material is a cardanol epoxy, an alkylated cardanol, analkoxylated cardanol, a cardanol allyl ether, an acrylated andmethacrylated cardanol, an isomerized cardanol, or a cardanol basedbenzoxazines.
 13. The method of claim 6, wherein the cardanol derivativeis a polymeric cardanol.
 14. The method of claim 13, wherein thepolymeric cardanol is a cardanol novolac, a cardanol resole, or acardanol-epoxy novolac.
 15. The method of claim 6, wherein the cardanolderivative is an epoxidized phenolated cardanol derivative.
 16. Themethod of claim 6, wherein the cardanol is epoxy functionalized on thephenoxy OH, on the alkyl side chain, or on both positions.
 17. A methodof producing a compound of claim 1, the method comprising reacting acardanol substrate with an unsaturated hydrolyzable silane in thepresence of the free radical initiator at a temperature ranging fromabout 100° C. to about 350° C. under an inert atmosphere that issubstantially free from water.
 18. The method of claim 17, wherein theunsaturated silane isvinyltrimethoxysilane, vinyltriethoxysilane,vinyltriacetoxysilane, allyl(methoxy)dimethylsilane,allyltriisopropoxysilane, allylphenyldiphenoxysilane, and anycombinations thereof.
 19. The method of claim 17, wherein the freeradical initiator is a peroxide catalyst in the group of benzoylperoxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxide)hexane, bis-(methylbenzoyl)peroxide, bis(dimethylbenzoyl) peroxide,dicumylperoxide, t-butyl 3-isopropenylcumyl peroxide, butyl4,4-bis(tert-butylperoxy)valerate, bis(trimethylbenzoyl)peroxide, andany combinations thereof.
 20. The method of claim 17, wherein the silaneis an amino-functional silane.
 21. The method of claim 20, wherein theamino-functional silanes is selected from the group consisting of3-aminopropyltriethoxysilane; bis[(3-triethoxysilyl)propyl]amine;3-aminopropyltrimethoxysilane; bis[(3-trimethoxysilyl)propyl]amine;3-aminopropylmethyl-diethoxysilane; 3-aminopropylmethyl-dimethoxysilane;aminoethylamino-propyl-trimethoxysilane; N-bis(3-(trimethylsiloxy)propyl)-1,2-ethanediamine;amino-ethyl-aminopropyl-triethoxysilane;amino-ethyl-aminopropyl-methyl-dimethoxysilane;diethylene-triamino-propyl-trimethoxysilane;diethylene-triamino-propyl-methyl-dimethoxysilane;piperazinyl-propyl-methyldimethoxysilane;(N-phenylamino)-methyl-triethoxysilane; and3-(N-phenylamino)-propyl-trimethoxysilane.
 22. The method of claim 17,wherein the silane comprise a hydrolyzable group selected from the groupconsisting of chloro, methoxy, propoxy, methylalkoxy, acetoxy, silazane,and oxime.
 23. (canceled)
 24. (canceled)